Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes

Autores
Deniz, Erhan; Tomasulo, Massimiliano; Cusido, Janet; Yildiz, Ibrahim; Petriella, Marco; Bossi, Mariano Luis; Sortino, Salvatore; Raymo, Françisco M.
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We synthesized five fluorophore-photochrome dyads designed to switch reversibly between nonfluorescent and fluorescent isomers under optical control. These compounds pair an oxazine photochrome to a biphenyl, fluorene, pyrene, coumarin, or cyanine fluorophore in their molecular skeleton and can be prepared in a single step from known precursors in yields ranging from 30 to 63%. Nuclear magnetic resonance spectroscopy indicates that the oxazine ring of these compounds opens and closes spontaneously on a millisecond time scale in acetonitrile at ambient temperature. Under these conditions, the fraction of ring-open isomer at equilibrium is negligible in all instances with the exception of the cyanine derivative, which instead is almost exclusively in this form. Absorption and emission spectroscopies demonstrate, however, that the fraction of ring-open isomer is sensitive to solvent polarity and increases with a transition from acetonitrile to methanol. Alternatively, the ring-open isomer can be populated photochemically or trapped with the addition of acid. In both instances, the characteristic absorption and emission bands of the 3H-indolium chromophores, embedded within the ring-open species, can clearly be observed in the visible region. In the case of the coumarin derivative, the brightness of this chromophoric fragment is sufficiently high to permit the imaging of individual molecules with excellent signal-to-noise ratios. In fact, the fluorescence of single fluorophore-photochrome dyads can be activated under the influence of ultraviolet inputs and the resulting species can be localized with nanoscale precision under visible illumination. Indeed, subdiffraction images of polymer nanoparticles, doped with this particular dyad, can be reconstructed with nanoscale resolution. Thus, our operating principles for fluorescence switching at the single-molecule level can offer the opportunity to overcome diffraction and, eventually, lead to the development of an entire family of probes for super-resolution fluorescence imaging. © 2012 American Chemical Society.
Fil: Deniz, Erhan. University of Miami; Estados Unidos
Fil: Tomasulo, Massimiliano. University of Miami; Estados Unidos
Fil: Cusido, Janet. University of Miami; Estados Unidos
Fil: Yildiz, Ibrahim. University of Miami; Estados Unidos
Fil: Petriella, Marco. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Bossi, Mariano Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Sortino, Salvatore. University of Catania; Italia
Fil: Raymo, Françisco M.. University of Miami; Estados Unidos
Materia
Fluorescence
Photochemistry
Photoswitching
Nanoscopy
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/67811

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network_name_str CONICET Digital (CONICET)
spelling Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine AuxochromesDeniz, ErhanTomasulo, MassimilianoCusido, JanetYildiz, IbrahimPetriella, MarcoBossi, Mariano LuisSortino, SalvatoreRaymo, Françisco M.FluorescencePhotochemistryPhotoswitchingNanoscopyhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We synthesized five fluorophore-photochrome dyads designed to switch reversibly between nonfluorescent and fluorescent isomers under optical control. These compounds pair an oxazine photochrome to a biphenyl, fluorene, pyrene, coumarin, or cyanine fluorophore in their molecular skeleton and can be prepared in a single step from known precursors in yields ranging from 30 to 63%. Nuclear magnetic resonance spectroscopy indicates that the oxazine ring of these compounds opens and closes spontaneously on a millisecond time scale in acetonitrile at ambient temperature. Under these conditions, the fraction of ring-open isomer at equilibrium is negligible in all instances with the exception of the cyanine derivative, which instead is almost exclusively in this form. Absorption and emission spectroscopies demonstrate, however, that the fraction of ring-open isomer is sensitive to solvent polarity and increases with a transition from acetonitrile to methanol. Alternatively, the ring-open isomer can be populated photochemically or trapped with the addition of acid. In both instances, the characteristic absorption and emission bands of the 3H-indolium chromophores, embedded within the ring-open species, can clearly be observed in the visible region. In the case of the coumarin derivative, the brightness of this chromophoric fragment is sufficiently high to permit the imaging of individual molecules with excellent signal-to-noise ratios. In fact, the fluorescence of single fluorophore-photochrome dyads can be activated under the influence of ultraviolet inputs and the resulting species can be localized with nanoscale precision under visible illumination. Indeed, subdiffraction images of polymer nanoparticles, doped with this particular dyad, can be reconstructed with nanoscale resolution. Thus, our operating principles for fluorescence switching at the single-molecule level can offer the opportunity to overcome diffraction and, eventually, lead to the development of an entire family of probes for super-resolution fluorescence imaging. © 2012 American Chemical Society.Fil: Deniz, Erhan. University of Miami; Estados UnidosFil: Tomasulo, Massimiliano. University of Miami; Estados UnidosFil: Cusido, Janet. University of Miami; Estados UnidosFil: Yildiz, Ibrahim. University of Miami; Estados UnidosFil: Petriella, Marco. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Bossi, Mariano Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Sortino, Salvatore. University of Catania; ItaliaFil: Raymo, Françisco M.. University of Miami; Estados UnidosAmerican Chemical Society2012-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/67811Deniz, Erhan; Tomasulo, Massimiliano; Cusido, Janet; Yildiz, Ibrahim; Petriella, Marco; et al.; Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes; American Chemical Society; Journal of Physical Chemistry C; 116; 10; 3-2012; 6058-60681932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp211796pinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp211796pinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:46:18Zoai:ri.conicet.gov.ar:11336/67811instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 09:46:18.554CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes
title Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes
spellingShingle Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes
Deniz, Erhan
Fluorescence
Photochemistry
Photoswitching
Nanoscopy
title_short Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes
title_full Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes
title_fullStr Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes
title_full_unstemmed Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes
title_sort Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes
dc.creator.none.fl_str_mv Deniz, Erhan
Tomasulo, Massimiliano
Cusido, Janet
Yildiz, Ibrahim
Petriella, Marco
Bossi, Mariano Luis
Sortino, Salvatore
Raymo, Françisco M.
author Deniz, Erhan
author_facet Deniz, Erhan
Tomasulo, Massimiliano
Cusido, Janet
Yildiz, Ibrahim
Petriella, Marco
Bossi, Mariano Luis
Sortino, Salvatore
Raymo, Françisco M.
author_role author
author2 Tomasulo, Massimiliano
Cusido, Janet
Yildiz, Ibrahim
Petriella, Marco
Bossi, Mariano Luis
Sortino, Salvatore
Raymo, Françisco M.
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Fluorescence
Photochemistry
Photoswitching
Nanoscopy
topic Fluorescence
Photochemistry
Photoswitching
Nanoscopy
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We synthesized five fluorophore-photochrome dyads designed to switch reversibly between nonfluorescent and fluorescent isomers under optical control. These compounds pair an oxazine photochrome to a biphenyl, fluorene, pyrene, coumarin, or cyanine fluorophore in their molecular skeleton and can be prepared in a single step from known precursors in yields ranging from 30 to 63%. Nuclear magnetic resonance spectroscopy indicates that the oxazine ring of these compounds opens and closes spontaneously on a millisecond time scale in acetonitrile at ambient temperature. Under these conditions, the fraction of ring-open isomer at equilibrium is negligible in all instances with the exception of the cyanine derivative, which instead is almost exclusively in this form. Absorption and emission spectroscopies demonstrate, however, that the fraction of ring-open isomer is sensitive to solvent polarity and increases with a transition from acetonitrile to methanol. Alternatively, the ring-open isomer can be populated photochemically or trapped with the addition of acid. In both instances, the characteristic absorption and emission bands of the 3H-indolium chromophores, embedded within the ring-open species, can clearly be observed in the visible region. In the case of the coumarin derivative, the brightness of this chromophoric fragment is sufficiently high to permit the imaging of individual molecules with excellent signal-to-noise ratios. In fact, the fluorescence of single fluorophore-photochrome dyads can be activated under the influence of ultraviolet inputs and the resulting species can be localized with nanoscale precision under visible illumination. Indeed, subdiffraction images of polymer nanoparticles, doped with this particular dyad, can be reconstructed with nanoscale resolution. Thus, our operating principles for fluorescence switching at the single-molecule level can offer the opportunity to overcome diffraction and, eventually, lead to the development of an entire family of probes for super-resolution fluorescence imaging. © 2012 American Chemical Society.
Fil: Deniz, Erhan. University of Miami; Estados Unidos
Fil: Tomasulo, Massimiliano. University of Miami; Estados Unidos
Fil: Cusido, Janet. University of Miami; Estados Unidos
Fil: Yildiz, Ibrahim. University of Miami; Estados Unidos
Fil: Petriella, Marco. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Bossi, Mariano Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Sortino, Salvatore. University of Catania; Italia
Fil: Raymo, Françisco M.. University of Miami; Estados Unidos
description We synthesized five fluorophore-photochrome dyads designed to switch reversibly between nonfluorescent and fluorescent isomers under optical control. These compounds pair an oxazine photochrome to a biphenyl, fluorene, pyrene, coumarin, or cyanine fluorophore in their molecular skeleton and can be prepared in a single step from known precursors in yields ranging from 30 to 63%. Nuclear magnetic resonance spectroscopy indicates that the oxazine ring of these compounds opens and closes spontaneously on a millisecond time scale in acetonitrile at ambient temperature. Under these conditions, the fraction of ring-open isomer at equilibrium is negligible in all instances with the exception of the cyanine derivative, which instead is almost exclusively in this form. Absorption and emission spectroscopies demonstrate, however, that the fraction of ring-open isomer is sensitive to solvent polarity and increases with a transition from acetonitrile to methanol. Alternatively, the ring-open isomer can be populated photochemically or trapped with the addition of acid. In both instances, the characteristic absorption and emission bands of the 3H-indolium chromophores, embedded within the ring-open species, can clearly be observed in the visible region. In the case of the coumarin derivative, the brightness of this chromophoric fragment is sufficiently high to permit the imaging of individual molecules with excellent signal-to-noise ratios. In fact, the fluorescence of single fluorophore-photochrome dyads can be activated under the influence of ultraviolet inputs and the resulting species can be localized with nanoscale precision under visible illumination. Indeed, subdiffraction images of polymer nanoparticles, doped with this particular dyad, can be reconstructed with nanoscale resolution. Thus, our operating principles for fluorescence switching at the single-molecule level can offer the opportunity to overcome diffraction and, eventually, lead to the development of an entire family of probes for super-resolution fluorescence imaging. © 2012 American Chemical Society.
publishDate 2012
dc.date.none.fl_str_mv 2012-03
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/67811
Deniz, Erhan; Tomasulo, Massimiliano; Cusido, Janet; Yildiz, Ibrahim; Petriella, Marco; et al.; Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes; American Chemical Society; Journal of Physical Chemistry C; 116; 10; 3-2012; 6058-6068
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/67811
identifier_str_mv Deniz, Erhan; Tomasulo, Massimiliano; Cusido, Janet; Yildiz, Ibrahim; Petriella, Marco; et al.; Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes; American Chemical Society; Journal of Physical Chemistry C; 116; 10; 3-2012; 6058-6068
1932-7447
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp211796p
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp211796p
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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